Water-soluble fiber-reactive sulphophanylazo-naphthyl dyestuffs containing an alpha, beta-dichloro- or dibrompropionylamino group

ABSTRACT

Fibre-reactive sulphophenylazonapthylmonoazo dyestuffs containing an Alpha , Beta -di-chloro- or dibromopropionylamino group. Yield on cotton brilliant dyeings of excellent general fastness-properties especially good fastness to light and excellant fastness to washing.

United States Patent De Montmollin et a1.

WATER-SOLUBLE FIBER-REACTIVE SULPHOPHANYLAZO-NAPHTHYL DYESTUFFSCONTAINING AN ALPHA, BETA-DICHLORO- OR DIBROMPROPIONYLAMINO GROUPInventors: Ren De Montmollin, Riehen; Henri Riot, Arlesheim, both ofSwitzerland Assignee: Ciba-Geigy A.G., Basel, Switzerland Filed: Nov.12, 1969 Appl. No.: 876,069

Related US. Application Data Continuation-impart of Ser. No. 753,829,July 22, 1968, abandoned, which is a continuation of Ser. No. 608,710,Nov. 1, 1966, abandoned, which is a division ofSer. No. 305,539, Aug.29, 1963, abandoned, which is a continuation-in-part of Ser. No.731,097, April 28, 1958, abandoned.

Foreign Application Priority Data May 7, 1957 Switzerland 45789/57 US.Cl 260/196, 8/50, 260/147, 260/149, 260/150, 260/151, 260/157, 260/161,260/162, 260/163, 260/174,

[51] Int. CL... C091) 62/00, C09b 62/04, D06p 3/66 [58] Field of Search260/196, 198, 199, 260/200, 201

[56] References Cited UNITED STATES PATENTS 2,973,351 2/1961 DeMontmollin et al. 2601199 3,007,762 11/1961 Wegrnann 61 al 260/199 x3,040,024 6/1962 Riat el al. 260/196 FOREIGN PATENTS OR APPLICATIONS613,644 1/1956 Germany 2601151 Primary Examiner-Floyd D. HigelAnorneyWenderoth, Lind & Ponack [5 7] ABSTRACT Fibre-reactivesulphophenylazonapthylmonoazo dyestuffs containing an a,B-di-chloroordibromopropionylamino group. Yield on cotton brilliant dyeings ofexcellent general fastness-properties especially good fastness to lightand excellant fastness to washing.

18 Claims, No Drawings WATER-SOLUBLE FIBER-REACTIVESULPHOPHANYLAZO-NAPHTHYL DYESTUFFS CONTAINING AN ALPHA, BETA-DICHLORO-OR DIBROMPROPIONYLAMINO GROUP CROSS-REFERENCE TO RELATED APPLICATIONSThis is a continuation-in-part application of our copending applicationSer. No. 753,829, filed July 22, 1968 and now abandoned, which was astreamlined continuation of our application Ser. No. 608,710, filed Nov.1, 1966, now abandoned, which itself was a division of our applicationSer. No. 305,539, filed Aug. 29, 1963, now abandoned, which in turn wasa continuation-in-part of our application Ser. No. 731,097, filed Apr.28, 1958, now abandoned.

This invention provides valuable new water-soluble azo dyestuffs whichcontain at least one aromatically bound a,B-dichloroordibromopropionylamino group. More especially it provideso-sulfobenzene-o'-hydroxy or -o'-aminomonoazo naphthalene dyestuffscontaining at least two and at most three sulfonic acid groups and atleast one and at most two aromatically bound azfl-dichloroordibromopropionylamino groups, which dyestuffs may be further substitutedin the benzene radical by lower alkyl, lower alkoxy, phenoxy,acetylamino, chlorine or bromine. Furthermore, it also providesbenzenemonoazosulfonaphthalene dyestuffs containing at least two and atmost three sulfonic acid groups and at least one and at most twoaromatically bound azfi-dichloro or dibromo propionylamino groups, whichdyestuffs may be further substituted in the benzene radical by amino,lower alkyl or lower alkoxy. The invention also provides o-sulfobenzeneor sulfonaphthalenemonoazo pyrazolone dyestuffs containing at least twoand at most three sulfonic acid groups and at I least one and at mosttwo aromatically bound azfi-dichloroor -dibromopropionylamino groups,which dyestuffs may be further substituted in the diazo component bylower alkyl, lower alkoxy, phenoxy, acylamino other thana,/3-dihalo-genpropionylamino, chlorine or bromine and in whichdyestuffs the coupling component is a 3-methyl or 3-carboxy-5-pyrazolonebound to the azo-linkage in 4-position.

Included in the invention are moreover complex chromium, cobalt orcopper compounds of monozao dyestuffs containing at least two and atmost three sulfonic acid groups and at least one and at most twoaromatically bound a2fi-dichloroor -dibromopropionylamino groups, whichdyestufi's correspond to the formula wherein R is the radical of ano-hydroxybenzene or an o-hydroxynaphthalene which may be furthersubstituted by lower alkyl, lower alkoxy, acylamino other thana,B-dihalogeno-propionylamino, chlorine or bromine and R, is the radicalof a hydroxyor aminonaphthalene bound to the azolinkage in o-position toa hydroxy or amino group or the radical of a 3-methylor3-carboxy-5-pyrazolone bound to the azo-linkage in 4- position. Furthercomplexes falling within this invention are chromium, cobalt or coppercomplexes of monoazodyestuffs containing at least two and at most threesulfonic acid groups and corresponding to the formula wherein Rrepresents a phenylor sulfophenyl-radical bound to the azobridge ino-position to the hydroxyl group and R, represents the radical of anaminonaphthol sulfonic acid bound to the azo linkage in vicinal positionto the hydroxyl group and bearing a azB-dichloro or dibromopropionylgroup on the amino group.

Finally, the instant invention also relates to disazodyestuffscontaining at least two and at most four sulfonic acid groups and atleast one and at most two aromati-cally bound azB-dichloroordibromopropionylamino groups, which dyestuffs correspond to the formulaII(') IIIH,

wherein R is an o-sulfobenzene radical which may be further substitutedby lower aklyl, lower alkoxy, tn'fluoromethyl, chlorine or bromine, oneX is hydrogen and the other X is a sulfonic acid group and R is abenzene radical which may be substituted by lower alkyl,trifluoromethyl, chlorine or bromine, sulfo or nitro. In the abovedefinition the term lower means: containing up to 4 carbon atoms.

Especially valuable groups of such dyestuffs are e.g.:

l. Dyestuffs of the general formula wherein A stands for a,B-dichloroordibromopropionyl, R for hydrogen or an optionally substituted loweralkyl radical, and D, for the radical of a diazo component whichcontains at least one sulfonic acid group and which also may contain anouB-di-chloroor di bromopropionylarnino group.

Valuable are e.g. diazo components in which the radical D, has theformula slogH S|O3H CHs- Cl- SOaH SIO H Cl CH3 SIOaH SIOJH SOaH whereinA has the aforecited meaning, one Y stands for SOaH and wherein thebenzene nucleus Z may contain further substituents, as e.g.

on3 0 on, NH-C 0cm 4. Monoazo dyestuffs with at least two sulfonic acidgroups of the general formula hydrogen and the other for a sulfonic acidgroup, and wherein A Possess the aforecited meaning, 4 Stands D standsfor the radical of a diazo component which may contain onewater-solubilizing group, e.g.

011 In) (IJII TIMI CO SOaH, HOaS- i CH or especially diazo components asmentioned above, which contain an a:B-dichloroor dibromopropionylaminogroup and/or a sulfo group.

3. Dyestuffs of the general formula H0 8 SOal'I OaH SlOaH for theradical of a diazo component, e.g.

whereby the sulfonic acid group is in ortho-position to the azo group,and K, stands for the radical of a hydroxynaphthalenesulfonic acid whichmay be further substituted, e.g.

SOaH

17H C O CH:

HO SOaH or a ketomethylene compound, e.g.

5. Dyestuffs of general formula wherein A and R possess the aforecitedmeanings, D stands for the radical of a diazo component which containsat least one sulfonic acid group and may contain an azo group, e.g.,

soul 0 0 OH H038 I SOaH SOzH sour SOaH cmoouN-C A-HN 1 H033 SIOCIH $0311IIOaS-C N=N or IIOKS- NH-A and K for the radical of a coupling compoundwhich couples in the adjacent position to an enolizable keto group, e.g.

and the dyestufi itself contains at least two sulfonic acid groups.

6. Metal complex compounds of monoazo dyestuffs having at least twoacid-solubilizing groups and at least one a,B-dichloroordibromopropionylamino group.

Suitable metal atoms are chromium, cobalt, nickel, and copper atoms, thelast-named being preferred.

The choice of diazo components for building dyestuffs of this typeincludes 2-aminol hydroxybenzenes, l-amino-Z-hydroxyand2-amino-lhydroxynaphthalenes, and Z-aminobenzenel carboxylic acids.Examples of suitable coupling compounds are l-(amino)aryl-5-pyrazolonesand aminohydroxynaphthalenesulfonic acids.

The a,B-dichloroor dibromo propionyl radical may be attached to thecoupling compound, for instance in the following combination:

N N C H0 33 H0 35 NA wherein R and A have the aforecited meanings, oraltematively to the diazo component, e.g.:

| g l N:N I Hols HOaS NIL-Q In addition the a,,8-dichloroordibromopropionyl radical may be attached to both the diazo-component andthe coupling-component, e.g. in the following combination wherein A andR possess the aforecited meanings.

Naturally 2:1 metal complexes as well as 1:1 complexes can be produced.The former contain preferably chromium or cobalt metal atoms.

The dyestuffs of this invention may be obtained from dyestuff componentswhich already contain the dihalogenated propionyl radical. Such dyestuffcomponents are obtainable by methods in themselves known, for example,by the acylation of appropriate compounds with a halide or anhydride ofan 64 :B-dihalogen-propionic acid.

Suitable compounds for this purpose are those which contain an easilyacylatable amino group, for example, a monoalkylamino group or a primaryamino group, and in the case of diazo-components, a less easilyacylatably primary amino group, and in the case of coupling componentseither a less easily acylatable amino group or a hydroxyl groupresponsible for coupling. As amino groups that are less readily acylatedthere may be mentioned principally those which occupy a position vicinalto an acid group, for example, a sulfonic acid group.Aminohydroxy-compounds are acylated in such manner that esterificationof the hydroxyl group is avoided.

Instead of introducing the aforesaid radicals into the dyestuffcomponents before the dyestufi is made, they may be introduced into thefinished dyestuffs. Thus, valuable dyestuffs containing anazB-dichloroor dibromopropionylamino group can be obtained by reacting adyestuff which contains an acylatable amino group, and above all a freeamino group, with, for example, azB-dichloroor dibromopropionic acidchloride or anhydride.

As soluble organic dyestuffs, which can be made in the above manner,there may be used metal-free or metalliferous monoazo-anddisazo-dyestuffs which latter may also be prepared by metallisation.Esepcially good results are obtained with soluble azodyestufi's whichpossess no affinity for cotton or at most no pronounced affinitytherefor. Such amino-azo-dyestuffs may be obtained, e.g., by hydrolysisof acylamino-azodyestuffs, by reduction of the nitro groups ofnitro-azodyestuffs or by coupling a diazotized aromatic amine with acoupling component containing an acylatable amino group.

As amines which, after diazotation, may be used as diazo components toproduce monoand disazo dyestuffs for use of the process of thisinvention, there may be mentioned for example:

aminobenzene, l-amino-2(3 or 4)-methylbenzene,

1-amino4-methoxybenzene-2-sulfonic acid,

l-aminobenzene-2(3 or 4)-suifonic acid,

l-aminobenzene-2,5(or 2,4 )-disulfonic acid, 3 (or 4 )-nitrol-aminobenzene, 4-nitro-1- aminobenzene-Z-sulfonic acid,

4 (or 5 )acetylaminol aminobenzene-2-sulfonic acid, 4- (or 3)acetylamino-l-aminobenzene,

4(01' 5) -nitro-2-hydroxy-1-aminobenzene,

6-acetylamino-2-hydroxy- 1 -aminobenzene-5 sulfonic acid,2-hydroxy-1-aminobenzene-4 (or 5 sulfonic acid,

2 (3 or 4)-aminobenzoic acid,

4-chloroacetylaminol -arninobenzene2-sulfonic acid,4-B-Chlorpropionylamino-l-aminobenzene-2- sulfonic acid,

3-trifluoromethyl-l -aminobenzene-6-sulfonic 3-trifluoromethyl-6-phenoxyl -aminobenzene,

methoxyl -aminobenzene-2-sulfonic acid,l-aminoazobenzene-2,4'-disulfonic acid, 4,4'-diaminodiphenyl-2,2 (or3,3')-disulfonic acid,

1 -amino-4-methyl (chloro-, bormoor phenoxy)-benzene-6-sul-fonic acid,l-aminonaphthalene-3 ,-disulfonic acid,2-aminonaphthalene-6,8-disulfonic acid,

Z-aminonaphthalene- 1 -sulfonic acid,

4,4 '-diamino-5 ,5 '-dimethyldiphenyl-2,2 '-disulfonic acid,

acid, 2-amino-4 (or 5 )-acetylamino4'-methyl-l :1

diphenylsulfone,

dibromo)- As coupling components which may be used to pro- 6 3-acetylamino-l -amino benzene,

3 -methoxy- 1 -aminobenzene,

3-dichloropropionylaminol -aminobenzene,

5 -methoxy-2-methyl 1 -aminobenzene,

l -amino-2-methoxybenzene N-ethyl-N-benzylphenylamino-sulfonic acid,

l,3-diaminobenzene-G-sulfonic acid,

meta-toluidine, 3-aminophenyl urea,

3-methyl-S-pyrazolone,

l (2 '-methyl 6-chlorophenyl )-3 -methyl-5 pyrazolone,

3-carboxy-5-pyrazolone,

l-phenyl-3-methyl-5-pyrazolone,

l-[2'-( or 3' or 4')-chlorophenyll-3-methyl-5- pyrazolone,

l [3(or -4 )-aminophenyll-3-carboxy-5-pyrazol0ne,

pyrazolone, l-(2'-chloro-5'-sulfophenyl)-3-methyl-5-pyrazolone,

l (2' ,5 -dichloro-4'-sulfophenyl )-3-methyl-5- pyrazolone,

barbituric acid,

acetoacetic acid ortho-anisidide,

aminonaphthalene-4 (5, 6, 7 or 8)-sulfonic acid,

1- or 2-hydroxynaphthalene,

l-hydroxynaphthalene-4 (or 5)-sulfonic acid,

2-hydroxynaphthalene-4(6, 7 or 8)-sulfonic acid,2-hydroxynaphthalene-3,6 (5,7 or 6,8)-disulfonic acid,

Z-aminonaphthalene-S (6, 7 or 8 )-sulfonic acid,

l-amino-8-hydroxynaphthalene-4,6-disulfonic acid,

l-hydroxynaphthalene-3,6 (or 4,8)-disulfonic acid,2-N-methylaminonaphthalene-6 (7 or 8)-sulfonic acid,

2-amino-8-hydroxynaphthalene-o-sulfonic acid,

2-N-methylamino-8-hydroxynaphthaleneb-sulfonic acid,l-amino-8-hydroxynaphthalene-3,fi-disulfonic acid,2amino-S-hydroxynaphthalene-7-sulfonic acid,2-N-methylamino-5-hydroxynaphthalene-7-sulfonie acid,

2-phenylamino8-hydroxynaphthalene-3 ',6-

disulfonic acid,

2-N-( 3 '-carboxyphenyl )amino-S- hydroxynaphthalene-7-sulfonic acid,

l-benzoylamino-8-hydroxynaphthalene-3,6 (or 4,6)-

disulfonic acid, 2-ureido-5-hydroxynaphthalene-7-sulfonic acid,2-carbethoxyarnino-5-hydroxynaphthalene-7- sulfonic acid,Z-B-methoxycarbethoxyamino-S- hydroxynaphthalene-7-sulfonic acid,l-(n-butyrylamino)-8-hydroxynaphthalene-3,6(or

4,6)-disulfonic acid l-acryloylamino-S-hydroxynaphthalene-3,6 (or 4,6)-

disulfonic acid 1 -B-chloropropionylamino-8-hydroxynaphthalene- 3,6(or4,6)-disulfonic acid 1 -chloroacetylarnino-8-hydroxynaphthalene-3 ,6(or

4,6)-disulfonic acid.

As examples of dyestuffs containing acylatable amino groups for use inthe process of this invention, to be acylated, for example, with adichloro or dibromopropionic acid halide or a corresponding acidanhydride, there may be mentioned the following (the acylatable aminogroup is italicized; the shade obtained with the acylated dyestuff isindicated in parenthesis):

21 4-amino-4'-(4-methoxy)-phenylazo-stilbene-2,2'-

disulfonic acid (orange), l-naphthyl-(2')-3-methyl-4-[4"-(4"-amin0)-phenyl]-pheny1azo-5-pyrazolone-4,8',2"- trisulfonic acid (brown-orange),1-phenyl-3-methyl-4-[4"-(3"'-amino)-phenyl-azo- 3 -methyl -phenylazo-5-pyrazolone-2 ',4 ',6' trisulfonic acid (orange-brown),l-phenyl-3-methyl-4-[4' '-(4' '-amin0)-phenylazo- 2 -methoxy-5 '-methyl]-phenylazo-5 -pyra.zo1one- 2',5,2'-trisulfonic acid (orange-brown),l-naphthyl-(2')-3-methyl-4-[4"-(4"'-amino)-phenylazo-3"-methyl]-phenylazo-5-pyrazolone- 4',8 ,2" '-trisulfonic acid(orange-brown), l-naphthyl-(2)-3-methyl-4-[4"-(4"'-amino)- phenylazo-3-methy1]-phenylazo-5-pyrazolone- 5',7',2"'-trisulfonic acid(orange-brown), 1-(4"-amin0)-stilbenyl-(4')-3-methyl-4-(4"-phenylazo)-phenylazo-5-pyrazolone- 2',2",2",4""-tetrasulfonic acid(orange-brown), 1-hydroxy-2-(4-phenylazo)-7-amino-naphthalene-3,2',4"-trisu1fonic acid (blue-red),l-(4-amino-2-methylsulfonylamino)-phenylazo-3-methyl-4-phenylazobenzene-2",4-disulfonic acid (orange-brown),

l-( 4 '-amin0-2 '-sulfoacetylamino )-phenylazo-3-methyl-4-phenylazobenzene-2",4"-disulfonic acid (orange-brown),

2-[4"-(4' -amin)-naphthyl-( 1 )-azo]- phenylazonaphthalene-4,6,8 ,7'-tetrasu1fonic acid (orange-brown),

2-[4'-(4' '-amin0-3 "-eth0xy)-naphthyl-(1")-azo]-phenylazonaphthalene-4,8 ,3 '-trisulfonic acid (orange-brown),

2-[4'-( 1"-hydroxy -6"amin0)-naphthyl-(2" )-azo- 2'-methy1]-phenylazonaphthalene-6,8 ,3 trisulfonic acid (blue-red),

l-[4-( l -hydroxy-6' '-amino)-naphthyl-(2")-azo]- naphthyl-( 1)-azobenzene-4,7,3 "-trisulfonic acid (blue-violet),

1-[4'-(4' -amino)-naphthyl-( l ")-azo-3-ethoxy]- naphthyl-( l)-azo-benzene-2,4,6"-trisulfonic acid (red-brown),

4-(4"-amin0-2"-methyl)-phenylazo-4'-( l hydroxy)-naphthyl-( 2' )-azo-3,3 -dimethyl-l ,1 diphenyl-6,6',4'"-trisulfonic acid (red),

4-(4"-amino-3"-methoxy-6"-methyl)-phenylazo-4'- l"-hydroxy)-naphthyl-(2" )-azo-1 ,1 -diphenyl- 2,2,4'",6"'-tetrasulfonicacid (red),

4-(4"-acetylamino)-phenylazo-4'-( l "'-hydroxy-6"'- amino)naphthyl-( 2)-azo-1 ,1 '-diphenyl- 2,2',3-trisulfonic acid (red),

4-(4"-amino-2"-methyl)-phenylazo-4-( 1"- hydroxy )-naphthyl-(2 )-azo-2,2'-dimethyl-1,l diphenyl-,3',6"'-trisulfonic acid (red),

4-(4"-amino-2"-sulfoacetylamino )-phenylazo-4- l -hydroxy )-naphthyl-( 2)-azo-2,2 "dimethyl- 1,1-diphenyl-5',4"'-disulfonic acid (red),4-(4"-amin0-2"-methyl)-phenylazo-4'-(2"'- hydroxy )-naphthy1)-(1")-azo-3,3 '-dimethyl-1 ,1 diphenyl-6,6',3",6'-tetra-sulfonic acid(red), 4- (4-amino-2 -methyl)-phenylazo-4'-( 1 '-hydroxy-8-amino)-naphthyl-(2' ')-azo-2,2 -dimethyl-l ,ldiphenyl-5,3"',6"'-trisulfonic acid (red-violet),

4-( 4 -amina-2 -acetylamino )-phenylazo-4 2 hydroxy)-naphthyl-(1"')-azo-l,l '-diphenyl-5,3 tetrasulfonic acid (red),

The acylation of such a dyestuff containing an acylatable amino groupwith one of the aforesaid dihalogenpropionic acid halides or anhydridesis advantageously carried out in the presence of an acidbinding agentsuch as sodium acetate, sodium hydroxide or sodium hydrogen carbonateand under relatively mild conditions, for example, in an organic solventor at a relatively low temperature in an aqueous medium.

The dyestuffs of this invention are new. They are suitable for dyeing orprinting especially polyhydroxylated materials of fibrous structure suchas cellulosic materials, and also synthetic fibers, for example, ofregenerated cellulose, or natural materials, for example, cellulose,linen or above all cotton. They are suitable for dyeing by the so-calleddirect dyeing methods and also by printing or foularding dyeing methods,especially from aqueous alkaline solutions, which may contain a highcontent of salts, for example, by the process in which the dyestuff isfixed on the material to be dyed by a heat treatment, for example, bysteaming, in the presence of an alkali, or preferably by storing thedyed or printed material at room-temperature or at a slightly elevatedtemperature, e.g., at a temperature between 15 and 40C for 1 to 24 hoursaccording to the socalled cold-pad-batch-process. Due to the reactivedihalogenopropionylamino substituent a chemical bonding is formedbetween the chromophore of the azo dyestuff and the cellulosic fiberduring the fixation process.

In order to remove non-fixed dyestuff and to improve the properties ofwet fastness of the dyeings so produced on cellulose fibers the dyeingsare thoroughly rinsed with cold and hot water. Advantageously they mayalso be treated with a dilute and advantageously slightly alkalineboiling solution of a nonionic detergent or a dispersing agent for ashort time, for example, 5-10 minutes.

Dyeings produced on cellulosic fibers with the dyestuffs of thisinvention are usually distinguished by the purity of their tints, bytheir good fastness to light and above all by their excellent fastnessto washing.

The following examples illustrate the invention, the parts andpercentages being by weight:

EXAMPLE 1 10.44 parts of the dyestufi of the formula s oin ON=NWCH3 HO NWhen the above dyestuff is acylated with 7.5 parts ofazB-dibromopropionyl chloride instead of 4.8. parts ofwfi-dichloropropionyl chloride, a product is obtained which likewisedyes cotton fast greenish yellow tints.

Example 2 8.76 parts of the dyestufi' of the formula OH SOaH SOQH areneutralized with sodium carbonate in 300 parts of water, and 6.56 partsof anhydrous sodium acetate are added. While stirring vigorously, asolution of 3.8 parts of azfi-dichloro propionyl chloride in 5 parts oftoluene is added dropwise at -5C within 10 minutes. After a short timethe acylation of the amino group is complete. The dyestuff is salted outwith 70 parts of sodium chloride, filtered off and dried in vacuo at 60to 70C. The dyestuff obtained in this manner dyes cotton bluish redtints.

When the above dyestuff is acylated with an equivalent amount ofazB-dibromopropionyl chloride instead Example 3 5.18 parts of thedyestuff of the formula H1) NH:

are neutralized with sodium carbonate in 300 parts of 5 water, and thissolution is mixed at room temperature dropwise with a solution of partsof azB-dichloropropionyl chloride in parts of acetone, and by thesimultaneous dropwise addition of aqueous sodium carbonate solution thepH value of the solution is maintained between 7 and 8. After completeacylation of the two amino groups the dyestuff is salted out with 100parts of sodium chloride and dried in vacuo at to C. The dyestuff dyescotton bluish-red tints.

By acylating the aminoazo dyestuffs in Column l withccB-dichloropropionyl chloride as described in the preceding Examplesfurther dyestuffs are obtained that dye cotton the tints shown in ColumnII.

@ N:: I I:

I ll

"N' N (i()()ll i u, Nu n0- N= H-c113 N NHg H0 \N/ T0311 no, N=N F0113I'm H i 2 I HO3S- w W (5H Reddish orange.

H03S- N=N Hols NH2 SOsH 4 W W i if 7 1 m Scarlet.

s03 Hols NH2 Yellow orsngzv.

Greonisli black.

By acylating the aminoazodyestuffs of Column I of the following table asdescribed in the preceeding examples, but with an equivalent amount ofazB-dibromopropionylchloride, further dyestuffs are obtained that dyecotton the tints shown in Column ll Example 4 53.0 parts of the dyestuffof the formula on no N=N NHQ 1IzN- 11038- S0311 35 parts of anhydroussodium acetate are added to the above solution which is then cooled toto 5C,

are neutralized with sodium carbonate in 750 parts of water. 12 parts byvolume of l0N S0dium hydroxide at that temperature, while stirringvigorously, a sosolution and 120 parts by volume of a sodium lution of35 parts of azfl-dichloropropionyl chloride is chromesalicylate solution(containing 2.8 parts of fidded dropwlse' 1 9" the sohmon f neutralchromium in 100 parts by volume) are added and the med and the dyestuffis obtained by evaporating the somixture is refluxed for 3 hours. Aftercooling, the soluhmon vacuotlOI't of the l:2-chrom ium complex so formedis neutral- The dyesmg dyes cotton covered vi 0] et tinw ized withhydrochloric acid.

The above solution is cooled to 0 to 5C and 40 parts By acylating themetalliferous azo dyestuffs listed in of anhydrous sodium acetate areadded. While stirring Column l with azB-dichloropropionyl chloride orvigorously, 40 parts of azB-dichloropropionyl chloride equivalentamounts of arB-dibromopropionyl chloride are added dropwise at 0 to 5Cwithin minutes. as described in Examples 4 and 5 there are obtainedAfter 2 hours the solution is neutralized with sodium dyestuffs that dyecotton the tints shown in Column ll.

i ll

1 Copper complex of the dycstufi of the formula: Ruby rod.

on 11c) HOQS -NI-I 2 1:2-chr0mium complex of the dyosluff of theformula: Bluish violet.

on no HOQS Nl 3 1:2-chromium complex of the dycstutl: Rcrlrlish blue.

on no II,N- N=N nois NH-Q s 03H '0 o n carbonate, and the dyestuff issalted out with sodium chloride and filtered off.

The dyestuff dyes cotton reddish grey tints. The parent dyestuff of theabove formula is obtain- Example 6 able, for example, by couplingdiazotized 5-nitro-2- aminophenol with hydroxynaphthalene-3:6-disulfonicacid and reducing the nitro group in the resulting dyestuff to an aminogroup by means of sodium hydrosulfide.

Z-phenylamino-S- 5 31.4 parts of4-(a:fi-dichloropropionylamino)-laminobenzene-2-sulfonic acid aredissolved in 600 parts of water with the addition of sodium carbonate.30 parts of hydrochloric acid of 30 percent strength are added at 0 to5C, and the mixture is diazotized with 25 parts by volume of 4Nsodiumnitrite solution. The diazo suspension, which gives an acid reaction toCongo, is then added to an ice-cold solution of 42.3 parts ofl-benzoylamino-8-hydroxy-naphthalene-3:6- disulfonic acid and 30 partsof sodium carbonate in 400 parts of water. On completion of the couplingthe dyestuff is salted out with sodium chloride, filtered off and driedin vacuo at 60 to C.

The resulting dyesturf of the formula H038 HOiS SO3H dyes cellulose bythe process described in Eirample 1 l red-violet tints.

If desired, the coupling can be carried out with advantage in thepresence of sodium acetate or sodium bicarbonate.

The 4-(azfidichloropropionylamino)- l aminobenzene-Z-sulfonic acid usedin this example can be prepared thus:

18.8 parts of l:4-diaminobenzene-2-sulfonic acid are dissolved in 400parts of water, and then neutralized with sodium carbonate. Whilestirring vigorously, 21 parts of mB-dichloropropionyl chloride are addeddropwise at to in the course of minutes, and at the same time thereaction solution is neutralized with dilute sodium carbonate solutionso as to maintain the reaction solution at a pH value of 6 to 7. Oncompletion of the reaction, the whole is acidified with hydrochloricacid, filtered, and the reaction product washed with saturated sodiumchloride solution.

in a similar manner 5-(mB-dichloropropionylamino)-l-aminobenzene-Z-sulfonic acid can be prepared from 5-amino-1-aminobenzene-2-sulfonic acid.

In the following Table further dyestuffs are listed which are obtainedaccording to the process described in Example 6 by coupling thediazotized amines listed in column 1 with the coupling components listedin column 2 and which yield on cotton dyeings having the shadesindicated in column 4. In this table the italicized amino-group meanseither an a,B-dichloropropionylamino group (I in column 3) or anafi-dibromopropionylamino group (ll in column 3). The diazo componentscorresponding to the indicated capital letters are the following:

A: aniline B: l-aminobenzene-2-sulfonic acid C:l,3-diaminobenzene-6-sulfonic acid D: l,4-diaminobenzene-6-sulfonic acidE: l-amino-4-methylbenzene-6 sulfonic acid F:l-amino-4-methoxybenzene-6-sulfonic acid G:l-amino-4-chlorobenzene-6-sulfonic acid H:l-amino-4-bromobenzene-6-sulfonic acid J:l,3-diamino-4-chlorobenzene-6-sulfonic acid K:1,3-diamino-4-methoxybenzene-fi-sulfonic acid L:l,3-diamin0-4-methylbenzene-6-sulfonic acid1-amino-4-phenoxybenzene-(S-sulfonic acid1,4-diamin0benzene-2,S-disulfonic acidl,4-diaminobenzene-2,fi-disulfonic acid 1,3-diaminobenzene-4,6-disulfonic acid l-aminobenzene-2,S-disulfonic acid1-aminobenzene-2,4-disulfonic acid Z-aminonaphthalene-4,8-disulfonicacid l-aminonaphthalene-3 ,6 -disulfonic acid-aminonaphthalene-5,7-disulfonic acid -aminonaphthalene-6,8-disulfonicacid -aminonaphthalene-4,6,8-trisulfonic acid M N O. P: Q: R: S: T: U:V: X: Y: -aminonaphthalene-1-sulfonic acid.

ll l -amino-8-hydroxynaphthalene- 3,6-disulfonic acid 6. D l bluishred7. E l red E n 9. F l 10. F ll l l. G l 12. G II l3. H I 14. H ll 15. Jl 16. K l 17. L l-ammo-' 8- ydroxg'naphthalenel red 3,6-disulfonlc acil8. M l 19. M ll 20. A l-amino-B- ydroignaphthalenel 4,6-disulfomc aci21. A ll 22. B l 23. B II 24. C l 25. D l bluishred 26. E 1 red 27. E ll28. F l 29. F ll 30. G l 31. G ll 32. H l 33. Hl-amino-8-hydroxynaphthalenell red 4,6-disulfonic acid 34. J l K n l 36.L l 37. M l 38. M ll 39. C l-gcetylaminofigal 3 6- ydroxynapenedisulfonic acid 40. D l bluishred M. J l red 42. K l 43. L l 44. Cl-N-benzoylamino-B- hydroxynaphthalene-3,6- disulfonic acid 1 bluishred45. .l H 46. K I 43. L I 44. C l-N-acetylamino-8-hydroxynaphthalene-4,6- dlsulfonic acid 1 red 45. D l-N-acetyiarnino-B-hydrcxynaphthalene-4,6- disulfonic acid I bluishred 46. J l red 47. K l48. L l 49. C l-N-butyrylamino-S- hydroxynaphthalene-4,6- disulfonicacid I 50 D u l 51. J l 52. K I 53. L I 54. C l-N-benzoylamnio-S-hydroxynaphthalene4,6- disulfonic acid I 55. D l 56. .l I bluishred 57.K 58. L l 59. C 2-ureido-5hydroxynaphthalene-7- sulfonic acid I orange60. C II 6]. D lI reddishorange By coupling the diazotised amines listedin column 1 with the coupling components listed in column 2 of thefollowing Table further dyestuffs are obtained, which

2. A monozao dysstuff of the formula
 3. A monoazo dyestuff of theformula
 4. A monozao dyestuff of the formula
 5. A monoazo dyestuff ofthe formula
 6. A monoazo dyestuff containing two or three sulfonic acidgroups and corresponding to the formula
 7. The monoazo dyestuffcorresponding to the formula
 8. The monoazo dyestuff corresponding tothe formula
 9. The monoazo dyestuff corresponding to the formula
 10. Themonoazo dyestuff of the formula
 11. The monoazo dyestuff of the formula12. The monoazo dyestuff of the formula
 13. The monoazo dyestuff of theformula
 14. The monoazo dyestuff of the formula
 15. The monoazo dyestuffof the formula
 16. The monoazo dyestuff of the formula
 17. The monoazodyestuff of the formula
 18. The monoazo dyestuff of the formula